WO2012070525A1 - 硬化性樹脂組成物及び硬化物 - Google Patents

硬化性樹脂組成物及び硬化物 Download PDF

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WO2012070525A1
WO2012070525A1 PCT/JP2011/076792 JP2011076792W WO2012070525A1 WO 2012070525 A1 WO2012070525 A1 WO 2012070525A1 JP 2011076792 W JP2011076792 W JP 2011076792W WO 2012070525 A1 WO2012070525 A1 WO 2012070525A1
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group
ladder
groups
resin composition
curable resin
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PCT/JP2011/076792
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French (fr)
Japanese (ja)
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禿恵明
井上慶三
不別博文
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株式会社ダイセル
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Priority to CN201180050103.3A priority Critical patent/CN103154145B/zh
Priority to KR1020137016336A priority patent/KR20140006811A/ko
Publication of WO2012070525A1 publication Critical patent/WO2012070525A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins

Definitions

  • the present invention relates to a curable resin composition and a sealant containing the same, a cured product thereof, an LED, and an optical semiconductor device.
  • a material having a heat resistance of 150 ° C. or higher is required as a material for covering a semiconductor element in a semiconductor device having a high heat resistance and a high withstand voltage.
  • a material for coating an optical material such as an LED element is required to have physical properties such as flexibility, transparency, heat yellowing resistance, and light yellowing resistance in addition to heat resistance.
  • the barrier property such as water vapor was low and the reliability was low.
  • At least one first organosilicon polymer having a crosslinked structure of siloxane (Si—O—Si bond) and at least one of linear connection structures of siloxane are used.
  • a synthetic polymer compound containing at least one kind of a third organosilicon polymer having a molecular weight of 20,000 to 800,000, which is formed by linking a second organosilicon polymer of a kind with a siloxane bond has been reported ( Patent Document 1).
  • Patent Document 1 specific methods for synthesizing these synthetic polymer compounds are not described, and the physical properties of these materials are not yet satisfactory.
  • a liquid silsesqui-foil having a cage structure containing an aliphatic carbon-carbon unsaturated bond and no H-Si bond At least one silsesquioxane selected from the group consisting of oxane and liquid silsesquioxane having a cage structure containing an H—Si bond and no aliphatic carbon-carbon unsaturated bond
  • Patent Document 2 A resin composition for sealing an optical element contained as a resin component is disclosed (Patent Document 2).
  • the hardened silsesquioxane cured product is relatively hard and lacks flexibility, so that cracks and cracks are likely to occur.
  • An object of the present invention is to provide a curable resin composition that provides a cured product having physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance.
  • Another object of the present invention is to provide an encapsulant for optical semiconductors that can obtain physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, light yellowing resistance after curing.
  • Another object of the present invention is to provide a cured product having physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance.
  • Another object of the present invention is to provide an LED having physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance.
  • Still another object of the present invention is to provide an optical semiconductor device excellent in various physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance and light yellowing resistance.
  • the inventors of the present invention cured a composition containing a ladder-type silsesquioxane, a linear polysiloxane having a specific molecular weight, and a hydrosilylation catalyst.
  • the present invention was completed by finding that a cured product having excellent physical properties such as property, flexibility, transparency, heat yellowing resistance and light yellowing resistance can be obtained.
  • the present invention relates to a ladder-type silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation, a linear polysiloxane (B) having a molecular weight of 100 to 9000, a hydrosilylation catalyst (C And a curable resin composition.
  • the curable resin composition of the present invention further comprises an isocyanuric acid compound capable of forming a carbon-silicon bond by hydrosilylation by reacting with the ladder-type silsesquioxane (A) and / or linear polysiloxane (B). (D) may be included.
  • the present invention also provides an encapsulant for optical semiconductors containing the curable resin composition.
  • the present invention also provides a cured product obtained by curing the curable resin composition.
  • the present invention further provides an LED including the cured product and an optical semiconductor device including the LED.
  • the curable resin composition contains a ladder-type silsesquioxane, a linear polysiloxane having a specific molecular weight, and a hydrosilylation catalyst. It progresses, and a cured product having excellent transparency, high temperature heat-resistant yellowing, and excellent flexibility is obtained. Even if this cured product is exposed to a high temperature of 150 ° C. or higher for a long period of time, it does not turn yellow and is excellent in flexibility. Therefore, the curable resin composition of the present invention is useful as a next-generation light source sealant. Further, according to the present invention, an LED and an optical semiconductor device excellent in various physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance can be obtained.
  • FIG. 2 is a graph showing the light transmittance of the cured product 1 obtained in Example 1.
  • the curable resin composition of the present invention comprises a ladder-type silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation, a linear polysiloxane (B) having a molecular weight of 100 to 9000, hydrosilyl Catalyst (C).
  • Ladder-type silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation and linear polysiloxane (B) having a molecular weight of 100 to 9000 include an aliphatic carbon-carbon double in the molecule.
  • Ladder-type silsesquioxane having a bond (hereinafter referred to as vinyl-type ladder silsesquioxane) and linear polysiloxane having an Si—H bond in the molecule (hereinafter referred to as Si—H-type linear polysiloxane)
  • Si—H-type linear polysiloxane a ladder-type silsesquioxane having a Si—H bond in the molecule
  • Si—H-type ladder silsesquioxane a ladder-type silsesquioxane having a Si—H bond in the molecule
  • a combination with linear polysiloxane (hereinafter referred to as vinyl linear polysiloxane) can be mentioned.
  • ladder-type silsesquioxane is a polysiloxane having a crosslinked three-dimensional structure.
  • Polysiloxane is a compound having a main chain composed of siloxane bonds (Si—O—Si), and the basic structural units thereof are represented by the following formulas (M), (D), (T), (Q) (hereinafter referred to as “polysiloxane”). , M unit, D unit, T unit, and Q unit).
  • R represents an atom or atomic group bonded to a silicon atom.
  • the M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom
  • the D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms.
  • the T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms
  • the Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms.
  • Silsesquioxane is a polysiloxane having the T unit as a basic structural unit, and its empirical formula (basic structural formula) is represented by RSiO 3/2 .
  • As the structure of the Si—O—Si skeleton of silsesquioxane a random structure, a ladder structure, and a cage structure are known.
  • the ladder-type silsesquioxane contained in the curable resin composition of the present invention is a silsesquioxane having a Si—O—Si skeleton having a ladder structure.
  • Ladder type silsesquioxane can be represented by the following formula (L), for example.
  • p is an integer of 1 or more (for example, 1 to 5000, preferably 1 to 2000, more preferably 1 to 1000).
  • Each R is the same or different and is a hydrogen atom, substituted or unsubstituted hydrocarbon group, hydroxyl group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, acyloxy group, mercapto group (thiol group), alkylthio Group, alkenylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group or substituted amino group (mono or dialkylamino group, acylamino group, etc.), epoxy group , A halogen atom, a group represented by the following formula (1), and the like.
  • Each R in the above formula (1) may be the same or different and is the same as R in the above formula (L).
  • Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • Examples of the alkyl group include C 1-20 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl, dodecyl groups (preferably C 1-10 alkyl groups, more preferably C 1-4 alkyl group).
  • alkenyl group examples include vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5- C 2-20 alkenyl groups such as a hexenyl group (preferably a C 2-10 alkenyl group, more preferably a C 2-4 alkenyl group).
  • alkynyl group examples include C 2-20 alkynyl groups such as ethynyl and propynyl groups (preferably C 2-10 alkynyl groups, more preferably C 2-4 alkynyl groups).
  • Examples of the alicyclic hydrocarbon group include C 3-12 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclododecyl groups; C 3-12 cycloalkenyl groups such as cyclohexenyl groups; bicyclohepta And C 4-15 bridged cyclic hydrocarbon groups such as nyl and bicycloheptenyl groups.
  • aromatic hydrocarbon group examples include C 6-14 aryl groups such as phenyl and naphthyl groups (particularly, C 6-10 aryl groups).
  • Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group.
  • Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include C 7-18 aralkyl groups such as benzyl and phenethyl groups (particularly C 7-10 aralkyl groups), and C 6-10 aryls such as cinnamyl groups.
  • the hydrocarbon group may have a substituent.
  • the carbon number of the substituent is 0 to 20, preferably 0 to 10.
  • the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydroxyl group; alkoxy group such as methoxy and ethoxy group; alkenyloxy group such as allyloxy group; aryloxy group such as phenoxy group; benzyl Aralkyloxy groups such as oxy groups; Acyloxy groups such as acetyloxy, propionyloxy, (meth) acryloyloxy, benzoyloxy groups; mercapto groups; alkylthio groups such as methylthio and ethylthio groups; alkenylthio groups such as allylthio groups; phenylthio groups Arylthio groups such as benzylthio groups; carboxyl groups; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbony
  • alkoxy group for R examples include C 1-6 alkoxy groups (preferably C 1-4 alkoxy groups) such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy groups and the like.
  • alkenyloxy group examples include a C 2-6 alkenyloxy group such as an allyloxy group (preferably a C 2-4 alkenyloxy group).
  • aryloxy group examples include a substituent such as a C 1-4 alkyl group, a C 2-4 alkenyl group, a halogen atom, and a C 1-4 alkoxy group on the aromatic ring such as phenoxy, tolyloxy, naphthyloxy group, and the like.
  • a C 6-14 aryloxy group which may be used.
  • the aralkyloxy group include C 7-18 aralkyloxy groups such as benzyloxy and phenethyloxy groups.
  • the acyloxy group include C 1-12 acyloxy groups such as acetyloxy, propionyloxy, and benzoyloxy groups.
  • alkylthio group examples include C 1-6 alkylthio groups (preferably C 1-4 alkylthio groups) such as methylthio and ethylthio groups.
  • alkenylthio group examples include a C 2-6 alkenylthio group (preferably a C 2-4 alkenylthio group) such as an allylthio group.
  • the arylthio group for example, the aromatic ring has a substituent such as a C 1-4 alkyl group, a C 2-4 alkenyl group, a halogen atom, a C 1-4 alkoxy group, etc., such as phenylthio, tolylthio, naphthylthio group, etc.
  • Examples thereof include C 6-14 arylthio group.
  • Examples of the aralkylthio group include C 7-18 aralkylthio groups such as benzylthio and phenethylthio groups.
  • Examples of the alkoxycarbonyl group include C 1-6 alkoxy-carbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and butoxycarbonyl groups.
  • Examples of the aryloxycarbonyl group include C 6-14 aryloxy-carbonyl groups such as phenoxycarbonyl, tolyloxycarbonyl, and naphthyloxycarbonyl groups.
  • Examples of the aralkyloxycarbonyl group include a C 7-18 aralkyloxy-carbonyl group such as a benzyloxycarbonyl group.
  • Examples of the mono- or dialkylamino group include mono- or di-C 1-6 alkylamino groups such as methylamino, ethylamino, dimethylamino, and diethylamino groups.
  • Examples of the acylamino group include C 1-11 acylamino groups such as acetylamino, propionylamino, and benzoylamino groups.
  • Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
  • each R is a hydrogen atom, a C 1-10 alkyl group (particularly a C 1-4 alkyl group), a C 2-10 alkenyl group (particularly a C 2 group). -4 alkyl group), C 3-12 cycloalkyl group, C 3-12 cycloalkenyl group, aromatic ring with C 1-4 alkyl group, C 2-4 alkenyl group, halogen atom, C 1-4 alkoxy group, etc.
  • Optionally substituted C 6-14 aryl group, C 7-18 aralkyl group, C 6-10 aryl-C 2-6 alkenyl group, hydroxyl group, C 1-6 alkoxy group, halogen atom Is preferred.
  • the ladder-type silsesquioxane occupies 50 mol% or more (more preferably 80 mol% or more, particularly preferably 90 mol% or more) of the substituted or unsubstituted hydrocarbon group in R in the formula (L). Is preferred.
  • a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (particularly an alkyl group having 1 to 4 carbon atoms such as a methyl or ethyl group), an aryl group having 6 to 10 carbon atoms (particularly a phenyl group), It is preferable that the aralkyl group having 7 to 10 carbon atoms (particularly benzyl group) occupies a total of 50 mol% or more (more preferably 80 mol% or more, particularly preferably 90 mol% or more).
  • Ladder type silsesquioxane can be manufactured by a well-known method.
  • the ladder-type silsesquioxane represented by the formula (L) is represented by the following formula (2): (In the formula, R is the same as above. Three X's are the same or different and each represents a hydrolyzable group or a hydroxyl group.) Or one or more hydrolyzable silane compounds represented by the formula (1) and the following formula (3) or (3 ′): ) (In the formula, R and X are the same as above. A plurality of R may be the same or different.) It can obtain by attaching
  • the hydrolyzable silane compound represented by formula (2) is used for forming a T unit of ladder-type silsesquioxane, and the silane compound represented by formula (3) or (3 ′) is end-capped. It functions as a stopper and is used to form M units of ladder-type silsesquioxane.
  • the hydrolyzable group in X may be a group capable of forming a siloxane bond by hydrolysis and silanol condensation, such as halogen atoms such as chlorine atom, bromine atom and iodine atom; methoxy, ethoxy, propoxy group and the like C 1-10 alkoxy group; C 1-10 acyloxy group such as acetyloxy, propionyloxy, benzoyloxy group and the like.
  • halogen atoms such as chlorine atom, bromine atom and iodine atom
  • methoxy, ethoxy, propoxy group and the like C 1-10 alkoxy group
  • C 1-10 acyloxy group such as acetyloxy, propionyloxy, benzoyloxy group and the like.
  • a chlorine atom and a C 1-4 alkoxy group are preferable.
  • the hydrolysis / condensation reaction is carried out, for example, by silanol condensation of the silane compound in water or a mixed solvent of water and an organic solvent in the presence of a silanol condensation catalyst, and during and after the reaction, the solvent and / or by-product ( Alcohol) and the like can be distilled off.
  • the reaction temperature is -78 ° C to 150 ° C, preferably -20 ° C to 100 ° C.
  • the amount of water used is 1 mol or more (for example, 1 to 20 mol, preferably 1 to 10 mol) with respect to 1 mol of the total silane compound.
  • organic solvent examples include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1, 2 Halogenated hydrocarbons such as dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; N, Amides such as N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benz
  • an acid catalyst or a base catalyst can be used as the silanol condensation catalyst.
  • the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid.
  • Sulfonic acids such as activated clay; solid acids such as activated clay; Lewis acids such as iron chloride.
  • the base catalyst examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as barium hydroxide and magnesium hydroxide; alkali metal carbonates such as sodium carbonate; barium carbonate Alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkaline earth metal alkoxides such as barium methoxide; sodium phenoxide and the like Alkali metal phenoxides; quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; tetramethylammonium hydroxide; Quaternary phosphonium hydroxides such as tetraalkylphosphonium hydroxides such as ruphosphonium hydroxide; triethylamine, N-methylpiperidine, 4-di
  • the reaction product can be separated and purified by separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
  • separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
  • the vinyl type ladder silsesquioxane is not particularly limited as long as it is a compound having a group having an aliphatic carbon-carbon double bond at the terminal or side chain of the ladder type silsesquioxane.
  • the ladder-type silsesquioxane represented by the formula (L) a compound in which at least one terminal R and / or at least one side R is a group having an aliphatic carbon-carbon double bond is exemplified. It is done.
  • Examples of the group having an aliphatic carbon-carbon double bond include vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3
  • a C 2-20 alkenyl group such as a pentenyl, 4-pentenyl, 5-hexenyl group (preferably a C 2-10 alkenyl group, more preferably a C 2-4 alkenyl group); a C 3-12 group such as a cyclohexenyl group A cycloalkenyl group; a C 4-15 bridged cyclic unsaturated hydrocarbon group such as a bicycloheptenyl group; a C 2-4 alkenyl-substituted aryl group such as a styryl group; and a cinnamyl group.
  • At least one of three Rs is the above C 2-20 alkenyl group, or a C 3-12 group. Also included are groups such as cycloalkenyl groups, C 4-15 bridged cyclic unsaturated hydrocarbon groups, C 2-4 alkenyl substituted aryl groups, cinnamyl groups, and the like.
  • the molecular weight of the vinyl-type ladder silsesquioxane is, for example, 100 to 800,000, preferably 200 to 100,000, more preferably 300 to 20,000, and particularly preferably 500 to 4000.
  • the molecular weight of the vinyl-type ladder silsesquioxane is within this range, it is liquid and has a low viscosity, so that it is highly compatible with Si—H type linear polysiloxane having a molecular weight of 100 to 9000 and is easy to handle.
  • the vinyl-type ladder silsesquioxane may be a mixture having various molecular weights within the above range.
  • the content of the aliphatic carbon-carbon double bond in the vinyl type ladder silsesquioxane is, for example, 0.0010 to 0.0040 mmol / g, preferably 0.0012 to 0.0030 mmol / g. Further, the ratio (by weight) of the aliphatic carbon-carbon double bond contained in the vinyl-type ladder silsesquioxane is, for example, 3.0 to 9.0%, preferably 3.7 to 5.7%.
  • Vinyl-type ladder silsesquioxane is a group having R having an aliphatic carbon-carbon double bond as a hydrolyzable silane compound represented by formula (2) in the method for producing ladder-type silsesquioxane. It can be produced by using at least a certain compound or using at least a compound in which at least one of R is a group having an aliphatic carbon-carbon double bond as the silane compound represented by the formula (3) or (3 ′). .
  • the vinyl-type ladder silsesquioxane is a ladder-type silsesquioxane (A1) having one or more hydrolyzable groups or hydroxyl groups as R in the ladder-type silsesquioxane represented by the formula (L). ) (Hereinafter sometimes simply referred to as “ladder-type silsesquioxane (A1)”) and the following formula (4): (In the formula, R is the same as above. Three Rs may be the same or different. However, at least one of R is a group having an aliphatic carbon-carbon double bond. X is hydrolysable. Group or hydroxyl group) It can manufacture by making 1 type or 2 types or more of the silane compounds (S1) represented by these react.
  • It has a hydrolyzable group in R of ladder-type silsesquioxane (A1), a hydrolyzable group in X of silane compound (S1) represented by formula (4), and an aliphatic carbon-carbon double bond in R
  • the group include the same hydrolyzable groups and groups having an aliphatic carbon-carbon double bond.
  • a C 1-4 alkoxy group such as methoxy or ethoxy group is particularly preferable.
  • the remaining R excluding the group having an aliphatic carbon-carbon double bond is the same or different, and is substituted or unsubstituted, having 1 to 10 alkyl groups (particularly alkyl groups having 1 to 4 carbon atoms such as methyl and ethyl groups), aryl groups having 6 to 10 carbon atoms (particularly phenyl groups), or aralkyl groups having 7 to 10 carbon atoms (particularly, A benzyl group).
  • silane compound (S1) represented by the formula (4) monohalogenated vinylsilane, monohalogenated allylsilane, monohalogenated 3-butenylsilane, monoalkoxyvinylsilane, monoalkoxyallylsilane, monoalkoxy-3- Examples include butenylsilane.
  • monohalogenated vinyl silanes include chlorodimethylvinyl silane, chloroethyl methyl vinyl silane, chloromethyl phenyl vinyl silane, chlorodiethyl vinyl silane, chloroethyl phenyl vinyl silane, chlorodiphenyl vinyl silane, and the like.
  • monohalogenated allylsilanes include allylchlorodimethylsilane, allylchloroethylmethylsilane, allylchloromethylphenylsilane, allylchlorodiethylsilane, allylchloroethylphenylsilane, allylchlorodiphenylsilane, and the like.
  • monohalogenated 3-butenylsilanes include 3-butenylchlorodimethylsilane, 3-butenylchloroethylmethylsilane, 3-butenylchloromethylphenylsilane, 3-butenylchlorodiethylsilane, and 3-butenyl.
  • Examples include chloroethylphenylsilane and 3-butenylchlorodiphenylsilane.
  • monoalkoxy vinyl silane examples include methoxy dimethyl vinyl silane, ethyl methoxy methyl vinyl silane, methoxy methyl phenyl vinyl silane, diethyl methoxy vinyl silane, ethyl methoxy phenyl vinyl silane, methoxy diphenyl vinyl silane, ethoxy dimethyl vinyl silane, ethoxy ethyl methyl vinyl silane, ethoxy methyl phenyl vinyl silane, Examples thereof include ethoxydiethylvinylsilane and ethoxyethylphenylvinylsilane.
  • Typical examples of monoalkoxyallylsilane include allylmethoxydimethylsilane, allylethylmethoxymethylsilane, allylmethoxymethylphenylsilane, allyldiethylmethoxysilane, allylethylmethoxyphenylsilane, allylmethoxydiphenylsilane, allylethoxydimethylsilane, allylethoxyethyl.
  • Examples include methylsilane, allylethoxymethylphenylsilane, allylethoxydiethylsilane, and allylethoxyethylphenylsilane.
  • monoalkoxy 3-butenylsilane examples include 3-butenylmethoxydimethylsilane, 3-butenylethylmethoxymethylsilane, 3-butenylmethoxymethylphenylsilane, 3-butenyldiethylmethoxysilane, and 3-butenylethyl.
  • the reaction between the ladder-type silsesquioxane (A1) and the silane compound (S1) represented by the formula (4) is usually performed in a solvent.
  • the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1,2-dichloroethane.
  • Halogenated hydrocarbons such as: ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate; N, N— Amides such as dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol, isopropyl alcohol, butanol, etc. Such as alcohol and the like. These solvents are used alone or in admixture of two or more.
  • the amount of the silane compound (S1) represented by the formula (4) is, for example, a total of 1 mol of reactive groups (hydrolyzable groups, hydroxyl groups) in the ladder-type silsesquioxane (A1), for example.
  • the amount is about 1 to 20 mol, preferably 2 to 10 mol, more preferably about 5 to 9 mol.
  • the reaction between the ladder-type silsesquioxane (A1) and the silane compound (S1) represented by the formula (4) is performed in the presence of a silanol condensation catalyst.
  • a silanol condensation catalyst those exemplified above can be used.
  • a base catalyst is preferably used as the silanol condensation catalyst.
  • the amount of the silanol condensation catalyst used is, for example, 0.1 to 10 mol, preferably 0.1 mol relative to the total of 1 mol of reactive groups (hydrolyzable group, hydroxyl group) in the ladder-type silsesquioxane (A1). 0.1 to 1.0 mol.
  • the amount of silanol condensation catalyst used may be a catalytic amount.
  • the reaction may be performed in the presence of a polymerization inhibitor.
  • the reaction temperature can be appropriately selected depending on the reaction components and the type of the catalyst, but is usually 0 to 200 ° C, preferably 20 to 100 ° C, more preferably 30 to 60 ° C.
  • the reaction may be carried out at normal pressure or under reduced pressure or pressure.
  • the reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
  • the reaction can be carried out by any method such as batch, semi-batch, and continuous methods.
  • the reactive group (hydrolyzable group such as alkoxy group, hydroxyl group) in the ladder-type silsesquioxane (A1) and the reactive group in the silane compound (S1) represented by the formula (4) is hydrolyzed / condensed (or condensed) to produce vinyl ladder silsesquioxane having an aliphatic carbon-carbon double bond in the corresponding molecule.
  • reaction product is separated by separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination of these. It can be purified.
  • the Si—H type ladder silsesquioxane is not particularly limited as long as the ladder type silsesquioxane has a Si—H bond at a terminal or a side chain thereof.
  • a compound in which at least one terminal R and / or at least one side R is a group having a hydrogen atom or a Si—H bond can be given.
  • the group having a Si—H bond include groups in which at least one of three Rs is a hydrogen atom in the group represented by the formula (1).
  • the molecular weight of the Si—H type ladder silsesquioxane is, for example, 100 to 800,000, preferably 200 to 100,000, more preferably 300 to 20,000, and particularly preferably 500 to 4000.
  • the Si—H type ladder silsesquioxane may be a mixture having various molecular weights within the above range.
  • the content of Si—H bonds in the Si—H type ladder silsesquioxane is, for example, 0.0001 to 0.005 mmol / g, preferably 0.0005 to 0.002 mmol / g. Further, the ratio (weight basis) of Si—H groups contained in the Si—H type ladder silsesquioxane is, for example, 0.01 to 0.30%, preferably 0.1 to 0.2%.
  • the Si—H type ladder silsesquioxane uses at least a compound in which R is a hydrogen atom as the hydrolyzable silane compound represented by the formula (2) in the method for producing the ladder type silsesquioxane,
  • the silane compound represented by the formula (3) or (3 ′) can be produced by using at least a compound in which at least one of R is a hydrogen atom.
  • the Si—H type ladder silsesquioxane is a ladder type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups as R in the ladder type silsesquioxane represented by the formula (L).
  • (A1) [Ladder-type silsesquioxane (A1)] and the following formula (5) (In the formula, R is the same as above. Three Rs may be the same or different. However, at least one of R is a hydrogen atom.
  • X represents a hydrolyzable group or a hydroxyl group.) It can manufacture by making 1 type or 2 types or more of silane compounds (S2) represented by these react.
  • the hydrolyzable group in R of the ladder-type silsesquioxane (A1) and the hydrolyzable group in X of the silane compound (S2) represented by the formula (5) are the same as the hydrolyzable groups described above. Can be mentioned.
  • As the hydrolyzable group in R of the ladder-type silsesquioxane (A1) a C 1-4 alkoxy group such as methoxy or ethoxy group is particularly preferable.
  • the remaining R excluding the hydrogen atom is the same or different and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (particularly methyl,
  • An alkyl group having 1 to 4 carbon atoms such as an ethyl group), an aryl group having 6 to 10 carbon atoms (particularly a phenyl group), or an aralkyl group having 7 to 10 carbon atoms (particularly a benzyl group) is preferable.
  • examples of the silane compound (S2) represented by the formula (5) include monohalogenated silane and monoalkoxysilane.
  • monohalogenated silanes include chlorodimethylsilane, chloroethylmethylsilane, chloromethylphenylsilane, chlorodiethylsilane, chloroethylphenylsilane, and chlorodiphenylsilane.
  • monoalkoxysilane examples include methoxydimethylsilane, ethylmethoxymethylsilane, methoxymethylphenylsilane, diethylmethoxysilane, ethylmethoxyphenylsilane, methoxydiphenylsilane, ethoxydimethylsilane, ethoxyethylmethylsilane, ethoxymethylphenylsilane, Examples thereof include ethoxydiethylsilane and ethoxyethylphenylsilane.
  • the reaction between the ladder-type silsesquioxane (A1) and the silane compound (S2) represented by the formula (5) is usually performed in a solvent.
  • a solvent the thing similar to the solvent used for reaction of the said ladder type silsesquioxane (A1) and the silane compound (S1) represented by Formula (4) can be used.
  • the amount of the silane compound (S2) represented by the formula (5) is, for example, a total of 1 mol of reactive groups (hydrolyzable groups, hydroxyl groups) in the ladder-type silsesquioxane (A1), for example.
  • the amount is about 1 to 30 mol, preferably about 1 to 10 mol, more preferably about 5 to 9 mol.
  • the reaction between the ladder-type silsesquioxane (A1) and the silane compound (S2) represented by the formula (5) is performed in the presence of a silanol condensation catalyst.
  • a silanol condensation catalyst an acid catalyst is usually used among the silanol condensation catalysts.
  • the basic catalyst is not preferable because it reacts with the silane compound (S2) represented by the formula (5).
  • the amount of the silanol condensation catalyst used is, for example, 0.001 to 1 mole, preferably 1 to 1 mole relative to a total of 1 mole of reactive groups (hydrolyzable group, hydroxyl group) in the ladder-type silsesquioxane (A1). 0.002 to 0.01 mol.
  • the amount of silanol condensation catalyst used may be a catalytic amount.
  • the reaction may be performed in the presence of a polymerization inhibitor.
  • the reaction temperature can be appropriately selected depending on the reaction components and the type of catalyst, but is usually ⁇ 78 ° C. to 120 ° C., preferably ⁇ 30 ° C. to 60 ° C., more preferably ⁇ 10 ° C. to 30 ° C.
  • the reaction may be carried out at normal pressure or under reduced pressure or pressure.
  • the reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
  • the reaction can be carried out by any method such as batch, semi-batch, and continuous methods.
  • the reactive group in the ladder-type silsesquioxane (A1) (hydrolyzable group such as alkoxy group, hydroxyl group) and the reactive group in the silane compound (S2) represented by the formula (5) (Hydrolysable group such as alkoxy group, hydroxyl group) is hydrolyzed / condensed (or condensed) to produce Si—H type ladder silsesquioxane having a Si—H bond in the corresponding molecule.
  • reaction product is separated by separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a combination of these. It can be purified.
  • those having an aliphatic carbon-carbon double bond or Si—H bond at the terminal are preferred because they tend to be excellent in compatibility in preparing the composition. Further, those having an aliphatic carbon-carbon double bond or Si—H bond in the side chain are preferred because they tend to be inexpensive.
  • Linear polysiloxane (B) having a molecular weight of 100 to 9000 The linear polysiloxane (B) having a molecular weight of 100 to 9000 contained in the curable resin composition of the present invention has a linear chain having a molecular weight of 100 to 9000 having a main chain composed of siloxane bonds (Si—O—Si).
  • a siloxane compound, a linear polysiloxane having an aliphatic carbon-carbon double bond in the molecule (vinyl type linear polysiloxane), and a linear polysiloxane having an Si—H bond in the molecule (Si—H).
  • Type linear polysiloxane Type linear polysiloxane).
  • the linear polysiloxane (B) having a molecular weight of 100 to 9000 can be represented by, for example, the following formula (6).
  • R is the same as described above. However, at least one of R is a group having an aliphatic carbon-carbon double bond or a hydrogen atom.
  • q is an integer of 1 or more (eg, 1 to 15, preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3). When q exceeds 15, compatibility with the ladder-type silsesquioxane (A) may deteriorate, which is not preferable.
  • each R is a hydrogen atom, a C 1-10 alkyl group (particularly a C 1-4 alkyl group), a C 2-10 alkenyl group (particularly a C 2 group). -4 alkyl group), C 3-12 cycloalkyl group, C 3-12 cycloalkenyl group, aromatic ring with C 1-4 alkyl group, C 2-4 alkenyl group, halogen atom, C 1-4 alkoxy group, etc.
  • Optionally substituted C 6-14 aryl group, C 7-18 aralkyl group, C 6-10 aryl-C 2-6 alkenyl group, hydroxyl group, C 1-6 alkoxy group, halogen atom Is preferred.
  • linear polysiloxane (B) examples include 1,1,3,3-tetramethylsiloxane, 1,1,3,3-tetramethyl-1,3-divinylsiloxane, 1,1,3,3 , 5,5-hexamethyltrisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,3, 3,5,5,7,7-octamethyl-1,7-divinyltetrasiloxane, 1,1,1,3,5,5,7,7,7-nonamethyltetrasiloxane, 1,1,1,3 , 5,5,7,7,7-Nonamethyl-3-vinyltetrasiloxane 1,1,1,3,5,7
  • linear polysiloxane (B) all or part of alkyl groups such as methyl groups of the above exemplified compounds are further substituted with aryl groups such as phenyl groups (preferably C 6-20 aryl groups).
  • aryl groups such as phenyl groups (preferably C 6-20 aryl groups).
  • the molecular weight of the linear polysiloxane (B) is 100 to 9000, preferably 100 to 7000, more preferably 100 to 5000, and particularly preferably 100 to 4000. When the molecular weight is within this range, a cured product having excellent compatibility with the ladder-type silsesquioxane (A) and excellent crack resistance can be obtained.
  • the said linear polysiloxane (B) can be used individually or in combination of 2 or more types.
  • the curable resin composition of the present invention may contain a polysiloxane other than the ladder-type silsesquioxane (A) and a linear polysiloxane (B) having a molecular weight of 100 to 9000.
  • hydrosilylation catalyst (C) examples include known hydrosilylation catalysts such as platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts.
  • platinum catalyst include a palladium catalyst or a rhodium catalyst containing a palladium atom or a rhodium atom instead of a platinum atom. These may be used alone or in combination of two or more. Of these, a platinum vinylmethylsiloxane complex is preferred because of its
  • the curable resin composition of the present invention is an isocyanuric acid compound (D) capable of forming a carbon-silicon bond by hydrosilylation by reacting with the ladder-type silsesquioxane (A) and / or linear polysiloxane (B). ) May be included.
  • isocyanuric acid compound (D) include an isocyanuric acid compound having an aliphatic carbon-carbon double bond in the molecule.
  • diallyl isocyanuric acid examples include allyl group-containing isocyanuric acid such as diallyl C 1-10 alkyl isocyanuric acid such as isocyanuric acid, diallylethyl isocyanuric acid and diallylmethyl isocyanuric acid.
  • An isocyanuric acid compound (D) may be used by 1 type, and may use 2 or more types together. Of these, diallyl isocyanuric acid and diallyl C 1-10 alkyl isocyanuric acid are preferable.
  • the content of the ladder-type silsesquioxane (A) is, for example, 45 to 98% by weight, preferably 50 to 95% by weight, more preferably 60 to 90% by weight, particularly preferably. Is 65 to 85% by weight.
  • the ratio of the ladder-type silsesquioxane (A) and the linear polysiloxane (B) having a molecular weight of 100 to 9000 is based on 1 mol of the aliphatic carbon-carbon double bond in the vinyl-type ladder silsesquioxane.
  • Si—H bond in Si—H type linear polysiloxane is 0.2 to 2 mol, especially 0.3 to 1.5 mol, especially 0.8 to 1.2 mol, or Si—H type ladder.
  • the weight ratio of the linear polysiloxane (B) is, for example, 3 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 100 parts by weight of the ladder type silsesquioxane (A). Is 10 to 100 parts by weight.
  • the content of the isocyanuric acid compound (D) is, for example, 0 to 10 parts by weight, preferably 0 to 8 parts by weight with respect to 100 parts by weight of the ladder-type silsesquioxane (A). Parts, more preferably 0.1 to 6 parts by weight.
  • the content of the isocyanuric acid compound (D) is in such a range, a cured product having excellent compatibility with the curable resin composition and excellent crack resistance when cured can be obtained.
  • the total amount of ladder-type silsesquioxane (A) and linear polysiloxane (B) is, for example, relative to the total amount of polysiloxane contained in the curable resin composition, It is 20% by weight or more, preferably 50% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the total amount of the ladder-type silsesquioxane (A) and the linear polysiloxane (B) is within this range, a cured product excellent in flexibility can be obtained.
  • the ratio of the total amount of the polysiloxane including the ladder type silsesquioxane (A) and the linear polysiloxane (B) is, for example, 50% by weight or more, preferably 80%. % By weight or more, more preferably 90% by weight or more.
  • the ratio of the total amount of polysiloxane is within this range, a cured product having particularly high heat resistance can be obtained.
  • the content of the hydrosilylation catalyst (C) is such that platinum, palladium, or rhodium in the catalyst is in the range of 0.01 to 1,000 ppm by weight. It is preferable that it is in the range of 0.1 to 500 ppm by weight.
  • the content of the hydrosilylation catalyst (C) is in such a range, the crosslinking rate is not significantly slowed, and there is less possibility of causing problems such as coloring in the crosslinked product, which is preferable.
  • the curable resin composition of the present invention may contain a hydrosilylation reaction inhibitor in order to adjust the speed of the hydrosilylation reaction.
  • a hydrosilylation reaction inhibitor include alkyne alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and phenylbutynol; 3-methyl-3-pentene Ene-in compounds such as 1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1, Examples include 3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, thiazole, benzothiazole, and benzotriazole.
  • the content of the hydrosilylation reaction inhibitor varies depending on the crosslinking conditions of the composition, but in practice, the content in the curable resin composition is preferably in the range of
  • the curable resin composition of the present invention as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, Inorganic fillers such as calcium carbonate, carbon black, silicon carbide, silicon nitride and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; silicone resins; Organic resin fine powders such as epoxy resins and fluororesins; fillers such as conductive metal powders such as silver and copper, solvents, stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, etc.) , Flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, crosslinking agents, reinforcing
  • the curable resin composition of the present invention can be obtained by stirring and mixing each of the above components at room temperature, for example.
  • the curable resin composition of the present invention includes a one-component system including a multi-component composition, and may be stored separately as a two-component or multi-component system and mixed before use.
  • the sealing agent of this invention contains the said curable resin composition.
  • the sealant of the present invention is excellent in physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance, and can be suitably used as a sealant for optical semiconductor elements and the like.
  • the curable resin composition of the present invention can be cured by a hydrosilylation reaction using the hydrosilylation catalyst (C).
  • the transparency does not change and further cracks do not occur, and the physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, light yellowing resistance, etc. Are better.
  • the water vapor barrier property is about 1/3 that of the conventional dimethyl silicone resin.
  • LEDs and optical semiconductor devices Since the LED of the present invention is sealed by the cured product having excellent physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, light yellowing resistance, etc., high temperature heat resistance, flexibility, transparency, Excellent physical properties such as heat yellowing resistance and light yellowing resistance.
  • the optical semiconductor device of the present invention includes an LED having excellent physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, light yellowing resistance, etc., the high temperature heat resistance, flexibility, and transparency are included. Excellent physical properties such as heat yellowing resistance and light yellowing resistance.
  • the ladder-type terminal ethoxy group phenylmethylsilsesquioxane used as a raw material was prepared by hydrolyzing and condensing triethoxymethylsilane and triethoxyphenylsilane (molar ratio 1: 1) by a conventional method.
  • Example 1 [Production of Ladder Silsesquioxane-containing Curable Resin Composition 1 Containing Isocyanuric Acid and Cured Product 1] 6.00 g of ladder-type vinylphenylmethylsilsesquioxane obtained in Synthesis Example 1, 0.30 g of diallylmethylisocyanuric acid (manufactured by Shikoku Kasei), 1,1,3,3,5,5-hexamethyltrisiloxane 1 .41 g (manufactured by Gelest) was weighed into a 6 ml screw tube and stirred at room temperature for 2 hours. As a result, a transparent and uniform solution with good compatibility was obtained.
  • Example 2 [Production of Ladder Silsesquioxane-Containing Curable Resin Composition 2 Containing Isocyanuric Acid and Cured Product 2] 0.60 g of ladder-type vinylphenylmethylsilsesquioxane obtained in Synthesis Example 1, 0.030 g of diallylmethyl isocyanuric acid (manufactured by Shikoku Kasei), 1,1,3,3,5,5,7,7-octa When 0.14 g of methyltetrasiloxane (manufactured by fluorochem) was weighed into a 6 ml screw tube and stirred for 2 hours at room temperature, a transparent and uniform solution with good compatibility was obtained.
  • Example 3 [Production of Ladder Silsesquioxane-Containing Curable Resin Composition 3 and Cured Product 3]
  • the ladder-type vinylphenylmethylsilsesquioxane (6.00 g) obtained in Synthesis Example 1 and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1.53 g, fluorochem) was weighed into a 6 ml screw tube and stirred at room temperature for 2 hours. As a result, a transparent and uniform solution with good compatibility was obtained. 6 ⁇ L of platinum vinylmethylsiloxane complex (manufactured by Wako Pure Chemicals; platinum 1.6 wt%) was charged into the obtained mixed liquid and stirred again to obtain a curable resin composition 3.
  • the obtained curable resin composition 3 was applied to a glass plate and heated in an oven at 60 ° C. for 1 hour and 150 ° C. for 5 hours, a colorless and transparent cured product 3 was obtained.
  • Example 4 [Production of Ladder Silsesquioxane-Containing Curable Resin Composition 4 and Cured Product 4] Weigh the ladder-type vinylphenylmethylsilsesquioxane (0.60 g) obtained in Synthesis Example 1 and 0.10 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Tokyo Chemical Industry) into a 6 ml screw tube. When the mixture was stirred for 2 hours at room temperature, a transparent and uniform solution with good compatibility was obtained. 0.6 ⁇ L of platinum vinylmethylsiloxane complex (manufactured by Wako Pure Chemicals; platinum 1.6 wt%) was added to the obtained mixed liquid and stirred again to obtain a curable resin composition 4. When the obtained curable resin composition 4 was applied to a glass plate and heated in an oven at 60 ° C. for 1 hour and 120 ° C. for 3 hours, a colorless and transparent cured product 4 was obtained.
  • a curable resin composition 4 was applied to
  • Example 5 [Production of Ladder Silsesquioxane-Containing Curable Resin Composition 5 and Cured Product 5]
  • the ladder-type phenylmethylsilsesquioxane vinyl derivative A (0.60 g) obtained in Synthesis Example 1 and 0.28 g of Si—H-terminated polysiloxane (manufactured by Gelest, molecular weight 400 to 500) are weighed into a 6 ml screw tube. When the mixture was stirred for 2 hours at room temperature, a transparent and uniform solution with good compatibility was obtained.
  • a curable resin composition 5 0.6 ⁇ L of a platinum vinylmethylsiloxane complex (manufactured by Wako Pure Chemicals; platinum 1.6 wt%) was charged into the obtained mixed liquid and stirred again to obtain a curable resin composition 5.
  • a curable resin composition 5 was applied to a glass plate and heated in an oven at 60 ° C. for 1 hour and at 120 ° C. for 3 hours, a colorless and transparent cured product 5 was obtained.
  • Example 6 [Production of Ladder Silsesquioxane-Containing Curable Resin Composition 6 and Cured Product 6]
  • Ladder type terminal trimethylsilyl group phenylmethylvinylsilsesquioxane (0.60 g) and 1,1,3,3-tetramethyldisiloxane 0.14 g (manufactured by Tokyo Chemical Industry) were weighed into a 6 ml screw tube for 2 hours. When stirred at room temperature, a transparent, uniform solution with good compatibility was obtained.
  • 0.6 ⁇ L of platinum vinylmethylsiloxane complex manufactured by Wako Pure Chemicals; platinum 1.6 wt%) was added to the obtained mixed solution and stirred again to obtain a curable resin composition 6.
  • the obtained curable resin composition 6 was applied to a glass plate and heated in an oven at 60 ° C. for 1 hour and at 120 ° C. for 3 hours, a colorless and transparent cured product 6 was obtained.
  • the ladder-type terminal trimethylsilyl group phenylmethylvinylsilsesquioxane used as the raw material of Example 6 is triethoxymethylsilane, triethoxyphenylsilane, and triethoxyvinylsilane (molar ratio 35:35:30) in a conventional manner. It was prepared by hydrolysis / condensation and terminal protection with chlorotrimethylsilane (vinyl group content average 8.0 wt%, molecular weight Mw 4200).
  • Example 7 3x2Al2O3 package (manufactured by Kyocera) for the package, OBL-CH2424 (manufactured by Genelites) for the LED element, KJR-3000M2 (manufactured by Shin-Etsu Silicone) for the die bond material, and SR-30 (manufactured by Tanaka Kikinzoku) for the gold wire Used to assemble LED package.
  • the curable resin compositions 1 to 6 obtained in Examples 1 to 6 were cured in the package (1 hour at 60 ° C., 5 hours at 150 ° C.) and fixed onto the lead wires of the universal substrate with solder, Samples for energization tests (resins 1 to 6) were produced.
  • Comparative Example A current test sample (epoxy resin) was prepared in the same manner as in Example 7 except that the curable resin composition was changed to an epoxy resin (CELVENUS W0910, manufactured by Daicel Chemical Industries, Ltd.).
  • the epoxy resin was energized continuously. After 1 week (after 168 hours), the discoloration of the resin, the change in light output, Vf (deterioration level of the device), cracks in the cured product (resin), and the presence or absence of peeling were visually confirmed. The results are shown in Table 2.
  • Resins 1 to 6 did not crack or peel off even when energized for 1 week. The epoxy resin was turned off in 52 hours.
  • the curable resin composition of the present invention When the curable resin composition of the present invention is thermally cured, a hydrosilylation reaction proceeds, and a cured product having excellent transparency, high-temperature heat-resistant yellowing, and flexibility is obtained. This cured product does not turn yellow even if it is exposed to a high temperature for a long period of time, and is excellent in flexibility. Therefore, it is difficult to cause cracks and cracks, and is therefore useful as a next-generation light source sealant.

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PCT/JP2011/076792 2010-11-25 2011-11-21 硬化性樹脂組成物及び硬化物 WO2012070525A1 (ja)

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